EP0235564A1 - Water-resistant photographic paper support - Google Patents

Water-resistant photographic paper support Download PDF

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Publication number
EP0235564A1
EP0235564A1 EP87101089A EP87101089A EP0235564A1 EP 0235564 A1 EP0235564 A1 EP 0235564A1 EP 87101089 A EP87101089 A EP 87101089A EP 87101089 A EP87101089 A EP 87101089A EP 0235564 A1 EP0235564 A1 EP 0235564A1
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EP
European Patent Office
Prior art keywords
fatty acid
paper
weight
anionic
photographic paper
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87101089A
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German (de)
French (fr)
Other versions
EP0235564B1 (en
Inventor
Alois-Bernhard Dr. Chem. Kerkhoff
Rudolf Dr. Dipl-Papier-Ing. Wanka
Wolfgang Storbeck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
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Publication of EP0235564A1 publication Critical patent/EP0235564A1/en
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/22—Polyalkenes, e.g. polystyrene
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes

Definitions

  • the invention relates to a photographic paper support, in particular a paper support which is suitable for receiving those black-and-white and color photographic layers which require wet development and fixation by means of photographic baths.
  • the photographic paper support is characterized by a highly smooth surface, a high internal strength and a slight soiling of the edges when treated with the photographic baths.
  • DOS 32 10 621 describes the use of a combination of alkyl ketene dimer or another neutral sizing agent, an anionic polyacrylamide and a cationic starch, DOS 32 16 841 an inner sizing of alkyl ketene dimer and cationic polyacrylamide and in DOS 32 16 840 a mixture of alkyl ketene dimer and a mixture of anionic and cationic polyacrylamide.
  • DOS 32 16 840 and DOS 32 16 841 also do not provide sufficiently smooth paper surfaces to be suitable for high-quality images.
  • the object of the invention is therefore to provide a photographic paper support which is suitable for the inclusion of photographic layers, in particular black / white and color photographic layers which require wet development and fixation, and which does not have the disadvantages associated with the prior art has, ie. which shows no significant contamination of the edges after treatment in photographic baths, even when using rapid development processes, and has a highly smooth surface.
  • the paper backing used in accordance with the invention is sized using fatty acids or fatty acid salts.
  • the fatty acids can be saturated or unsaturated. They contain 14 to 20 carbon atoms and are e.g. Palmitic acid, stearic acid or oleic acid. Fatty acids with 16 to 18 carbon atoms, especially stearic acid and their salts, e.g. Sodium stearate.
  • the sizing agents are added to the paper pulp in an acidic pH range from 3.5 to 5 using aluminum salts, preferably aluminum sulfate or aluminum chloride.
  • alkyl ketene dimer can be added to this sizing mixture of fatty acid and / or fatty acid salt and aluminum salt.
  • the alkyl ketene dimers used contain alkyl groups with 12 to 18 carbons atoms and can be used individually or as a mixture.
  • an epoxidized higher fatty acid amide is further added to the paper pulp.
  • the fatty acid residues of the epoxidized higher fatty acid amide consist of alkyl groups with 14 to 30 carbon atoms.
  • the ratio of epoxidized higher fatty acid amide to fatty acid or the fatty acid salt is 0.01: 1 to 0.2: 1. If alkyl ketene dimer is additionally used, the ratio of epoxidized higher fatty acid amide to alkyl ketene dimer to fatty acid or fatty acid salt is 0.02: 0.2: 1 to 0.15: 0.4: 1.
  • the total amount of epoxidized higher fatty acid amide which is added to the sizing mixture used according to the invention is 0.01 to 0.3% by weight, based on the paper pulp. If epoxidized higher fatty acid amide is added to the paper pulp in amounts below 0.01% by weight, based on the paper pulp, the penetration of the photographic baths into the paper is not sufficiently prevented. If the amount of epoxidized higher fatty acid amide is increased to over 0.3% by weight, based on the pulp, the paper loses its internal strength, which has a negative effect on the properties as a support for photographic layers.
  • Anionic and cationic polyacrylamide are also added to the paper pulp.
  • the ratio of anionic to cationic polyacrylamide is 40/60 to 60/40, preferably exactly 50/50.
  • the total amount added is 0.2 to 2.0% by weight, preferably 0.4 to 1.4 wt .-%, based on the pulp.
  • Examples of cationic polyacrylamides which are used according to the invention are products of polyacrylamides modified according to Mannich, Hofmann degradation products of polyacrylamides, copolymerization products between acrylamides and ethyleneimine, copolymers of acrylamide with a cationic monomer, such as dimethylaminoethyl methacrylate, in the form of the acidic salts of organic or mineral acids or in quaternized form with methyl chloride or dimethyl sulfate, or esters such as Diethylaminoethyl acrylate.
  • the molecular weight is in a range from 500,000 to 2,000,000, preferably from 1,000,000 to 1,500,000.
  • Anionic polyacrylamides used according to the invention are e.g. partially hydrolyzed products of polyacrylamides, acrylamide / acrylic acid copolymers or their salts, (meth) acrylamide / methacrylic acid copolymers or their salts, (meth) acrylamide (meth) acrylic acid / acrylonitrile copolymers or their salts and (Meth) acrylamide / (meth) acrylic ester copolymers or their saponification products.
  • the molecular weight is in the range from 500,000 to 2,000,000, preferably from 1,000,000 to 1,500,000.
  • anionic and cationic polyacrylamide does not cause strong flocculation of the fibers, but rather a highly smooth surface of the paper with a simultaneous drastic increase in the internal strength.
  • the increase in strength proved to be not only dependent on the concentration. In general, a concentration-dependent increase in the internal strength could be observed for all polyacrylamide combinations used, but this gain in strength was different with the same amounts used, the same quantity ratio and the same chain lengths of the polyacrylamides.
  • the polyacrylamides used according to the invention can be added to the paper pulp as a mixture or individually. The individual addition is preferred.
  • the paper can also be provided with a surface sizing consisting, for example, of a starch or polyvinyl alcohol coating which is applied to the paper web from an aqueous solution using a known application method.
  • the paper can also be provided on one or both sides with a polyolefin coating layer, which can contain a light-reflecting white pigment (especially in the front coating) and, if appropriate, color pigments, optical brighteners and / or other additives such as antistatic compounds, dispersing aids for the white pigment and antioxidants.
  • the polyolefin coating layer is applied in a conventional manner by extrusion coating.
  • the paper itself can also contain mineral or organic fillers, white pigment, dye or color pigment, optical brighteners, antioxidants and / or other additives customary in the production of photographic supports.
  • the paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.
  • the paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.
  • the paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.
  • the paper made from this mixture is extrusion coated with polyethylene in the usual way.
  • the paper made from this mixture is provided with a surface coating of the following composition: Water 1000 g Crotonic acid-modified polyvinyl alcohol degree of saponification: 99% Carboxyl group content 3.1 mol% 40 g Zirconium ammonium carbonate 8 g Sodium chloride 20 g
  • the order quantity is 2 g / m2.
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • the paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.
  • the paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.
  • An approx. 150 g / m2 heavy paper is produced according to Example 1 of DOS 32 10 621 from an aqueous cellulose slurry, to which a sizing mixture of the following composition has been added: Alkyl ketene dimer 0.5% by weight epoxidized higher fatty acid amide 0.3% by weight cationic starch 2.5% by weight anionic polyacrylamide 0.3% by weight
  • the paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.
  • the paper made from this mixture is extrusion coated with polyethylene in the usual way.
  • Test 1 Measurement of surface smoothness (number of surfaces)
  • test is carried out on the uncoated paper using the test method described in German patent application P 34 26 782.4-52.
  • the polyethylene coated paper is subjected to a simulated photographic development process with a commercial developer containing benzyl alcohol at a temperature of about 30 ° C and for a period of 25 minutes.
  • the penetration of the photographic baths is measured on both edges of the test piece with a measuring magnifier. The measured values are given as edge penetration (KE) in mm.
  • Test 3 Determination of the internal strength (gap strength)
  • the test is carried out on the paper coated with polyethylene according to the method specified in TAPPI RC 308 with the Internal Bond Impact Tester Model B. The measurements are reported in 1/1000 feet x pounds.
  • Examples 1 to 5 illustrate the effect according to the invention.
  • the test values in column 3 show that the optimum in terms of the internal strength of the paper is 10% with an anionic group in the anionic polyacrylamide.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

Beschrieben wird ein wasserfester fotografischer Papierträger, der mit einem Polyolefinharz beschichtet ist, dessen Papier aus einer besonderen Papiermasse gebildet ist, die Fettsäure und/oder Fettsäuresalze und Aluminiumsalz sowie gegebenenfalls einen Alkylketendimer enthält. Die Papiermasse enthält außerdem anionisches und kationisches Polyacrylamid im Verhältnis 40 : 60 bis 60 : 40 sowie ein epoxidiertes höheres Fettsäureamid. Der Anteil der anionischen Gruppen im anionischen Polyacrylamid beträgt 5 - 20 %.A waterproof photographic paper support is described which is coated with a polyolefin resin, the paper of which is formed from a special paper pulp which contains fatty acid and / or fatty acid salts and aluminum salt and optionally an alkyl ketene dimer. The paper pulp also contains anionic and cationic polyacrylamide in a ratio of 40:60 to 60:40 and an epoxidized higher fatty acid amide. The proportion of anionic groups in the anionic polyacrylamide is 5-20%.

Description

Die Erfindung betrifft einen photographischen Papierträger , insbesondere einen Papierträger , der zur Aufnahme solcher schwarz-weiß- und farbphoto­graphischer Schichten geeignet ist , die einer Naßentwicklung und -fixierung durch photographische Bäder bedürfen . Der photographische Papierträger zeichnet sich durch eine hochglatte Oberfläche , eine hohe innere Festigkeit und ein geringes Verschmutzen der Kanten bei der Behandlung mit den photographischen Bädern aus .The invention relates to a photographic paper support, in particular a paper support which is suitable for receiving those black-and-white and color photographic layers which require wet development and fixation by means of photographic baths. The photographic paper support is characterized by a highly smooth surface, a high internal strength and a slight soiling of the edges when treated with the photographic baths.

Die Verwendung von Papier als Träger für photogra­phische Schichten ist seit langem bekannt und in mancher Hinsicht auch vorteilhaft . Nachteilig ist jedoch die hohe Absorptionsfähigkeit des Papieres für photographische Bäder . Durch die neuen Schnellentwicklungsverfahren wird die Wässerung des Papierträgers verkürzt und die im Papier verbleibenden photographischen Behandlungs­lösungen können im Laufe der Zeit oder durch Ein­wirkung von Wärme bräunliche Verfärbungen bilden , die zu einer Beeinträchtigung des Bildes führen .The use of paper as a support for photographic layers has long been known and is also advantageous in some respects. A disadvantage, however, is the high absorbency of the paper for photographic baths. The new rapid development processes shorten the watering of the paper support and the photographic treatment solutions remaining in the paper can form brownish discolourations over time or under the influence of heat, which lead to an impairment of the image.

Die übliche Beschichtung des Papierträgers mit Polyolefinen schützt zwar dessen Oberflächen , die Kanten , die durch das Schneiden entstehen , bleiben jedoch gegenüber der Einwirkung der photographischen Bäder ungeschützt .The usual coating of the paper support with polyolefins protects its surfaces, but the edges that result from cutting remain unprotected against the effects of the photographic baths.

Um die Verschmutzung der Kanten zu verringern , ist es bekannt , das Papier mit neutralen Leimungs­mitteln , z.B. Alkylketendimeren , zu leimen . Die Verwendung dieser neutralen Leimungsmittel reicht jedoch nicht aus , um die Kanten des Papierträgers in Schnellentwicklungsverfahren vollständig zu schützen .In order to reduce the contamination of the edges, it is known to glue the paper with neutral sizing agents, for example alkyl ketene dimers. However, the use of these neutral sizing agents is not sufficient to completely protect the edges of the paper carrier in rapid development processes.

Speziell die Permeation des in den meisten handelsüblichen Entwicklern enthaltenen Alkohols , z.B. Benzylalkohol , wird nicht ausreichend verhindert .Especially the permeation of the alcohol contained in most commercial developers, e.g. Benzyl alcohol is not sufficiently prevented.

Es sind verschiedene Wege aufgezeigt worden , ein mittels neutraler Leimungsmittel geleimtes Papier durch weitere Zusätze umempfindlich gegenüber der Einwirkung des Alkohols zu machen .Various ways have been shown to make a paper sized by means of neutral sizing agents sensitive to the effects of alcohol by means of further additives.

In DOS 32 10 621 wird die Verwendung einer Kombi­nation aus Alkylketendimer oder einem anderen neutralen Leimungsmittel , einem anionischen Poly­acrylamid und einer kationischen Stärke beschrieben, in DOS 32 16 841 eine Innenleimung aus Alkylketen­dimer und kationischem Polyacrylamid und in DOS 32 16 840 ein Gemisch aus Alkylketendimer und einer Mischung von anionischem und kationischem Polyacrylamid .DOS 32 10 621 describes the use of a combination of alkyl ketene dimer or another neutral sizing agent, an anionic polyacrylamide and a cationic starch, DOS 32 16 841 an inner sizing of alkyl ketene dimer and cationic polyacrylamide and in DOS 32 16 840 a mixture of alkyl ketene dimer and a mixture of anionic and cationic polyacrylamide.

Die in DOS 32 10 621 beschriebene Verfahrensweise liefert zwar in Bezug auf die Verschmutzung der Kanten durch die photographischen Bäder recht brauchbare Ergebnisse , nachteilig ist jedoch die Beeinträchtigung der Oberflächengüte des Papiers .The procedure described in DOS 32 10 621 delivers quite useful results with regard to the soiling of the edges by the photographic baths, but the disadvantage is the impairment of the surface quality of the paper.

Auch die in DOS 32 16 840 und DOS 32 16 841 beschriebenen Verfahrensweisen liefern keine genügend glatten Papieroberflächen , um für qualitativ hochwertige Bilder geeignet zu sein .The procedures described in DOS 32 16 840 and DOS 32 16 841 also do not provide sufficiently smooth paper surfaces to be suitable for high-quality images.

Durch Leimung des Papierkerns mit einer bekannten sauren Leimung unter Verwendung von Fettsäure und/oder Fettsäuresalzen und Aluminiumsulfat wird zwar eine gute Oberfläche erhalten ,das Eindringen der photographischen Bäder wird jedoch nicht aus­ reichend verhindert , sodaß die Kanten solcher mit Fettsäure und Aluminiumsalzen geleimten Papiere be­sonders stark verschmutzen .By sizing the paper core with a known acid sizing using fatty acid and / or fatty acid salts and aluminum sulfate, a good surface is obtained, but the penetration of the photographic baths is not prevented sufficiently prevented so that the edges of such papers glued with fatty acid and aluminum salts become particularly dirty.

Aufgabe der Erfindung ist es daher , einen photo­graphischen Papierträger zu schaffen , die für die Aufnahme photographischer Schichten , insbesondere schwarz/weiß- und farbphotographischer Schichten , die einer Naßentwicklung und -fixierung bedürfen , geeignet ist und der die mit dem Stand der Technik verbundenen Nachteile nicht aufweist , dh. der nach der Behandlung in photographischen Bädern , auch bei der Verwendung von Schnellentwicklungsverfahren , keine nennenswerte Verschmutzung der Kanten zeigt und eine hochglatte Oberfläche besitzt .The object of the invention is therefore to provide a photographic paper support which is suitable for the inclusion of photographic layers, in particular black / white and color photographic layers which require wet development and fixation, and which does not have the disadvantages associated with the prior art has, ie. which shows no significant contamination of the edges after treatment in photographic baths, even when using rapid development processes, and has a highly smooth surface.

Die Aufgabe wird durch die in den Ansprüchen beschriebenen Merkmale gelöst .The object is achieved by the features described in the claims.

Der erfindungsgemäß verwendete Papierträger wird unter Verwendung von Fettsäuren oder Fettsäuresalzen geleimt . Die Fettsäuren können gesättigt oder unge­sättigt sein . Sie enthalten 14 bis 20 Kohlenstoff­atome und sind z.B. Palmitinsäure , Stearinsäure oder Ölsäure . Bevorzugt werden Fettsäuren mit 16 bis 18 Kohlenstoffatomen , speziell Stearinsäure sowie deren Salze , z.B. Natriumstearat, eingesetzt. Der Zusatz der Leimungsmittel erfolgt zur Papier­masse in einem sauren pH-Bereich von 3,5 bis 5 unter Verwendung von Aluminiumsalzen , bevorzugt Alumini­umsulfat oder Aluminiumchlorid .The paper backing used in accordance with the invention is sized using fatty acids or fatty acid salts. The fatty acids can be saturated or unsaturated. They contain 14 to 20 carbon atoms and are e.g. Palmitic acid, stearic acid or oleic acid. Fatty acids with 16 to 18 carbon atoms, especially stearic acid and their salts, e.g. Sodium stearate. The sizing agents are added to the paper pulp in an acidic pH range from 3.5 to 5 using aluminum salts, preferably aluminum sulfate or aluminum chloride.

Dieser Leimungsmischung aus Fettsäure und/oder Fettsäuresalz und Aluminiumsalz kann ein Alkylketen­dimer zugesetzt werden . Die verwendeten Alkylketen­dimer enthalten Alkylgruppen mit 12 bis 18 Kohlen­ stoffatomen und können einzeln oder auch als Gemisch eingesetzt werden .An alkyl ketene dimer can be added to this sizing mixture of fatty acid and / or fatty acid salt and aluminum salt. The alkyl ketene dimers used contain alkyl groups with 12 to 18 carbons atoms and can be used individually or as a mixture.

Erfindungsgemäß wird der Papiermasse weiterhin ein epoxidiertes höheres Fettsäureamid zugesetzt . Die Fettsäurereste des epoxidierten höheren Fettsäureamids bestehen aus Alkylgruppen mit 14 bis 30 Kohlenstoff-Atomen .
In einer sauer geleimten Papiermasse beträgt das Verhältnis von epoxidiertem höheren Fettsäureamid zur Fettsäure bzw. dem Fettsäuresalz 0,01 : 1 bis 0,2 : 1 .
Bei zusätzlicher Verwendung von Alkylketendimer be­trägt das Verhältnis von epoxidiertem höherem Fett­säureamid zu Alkylketendimer zu Fettsäure bzw. Fettsäuresalz 0,02 : 0,2 : 1 bis 0,15 : 0,4 : 1 . Die Gesamtmenge an epoxidiertem höheren Fettsäure­amid , die der erfindungsgemäß verwendeten Leimungs­mischung zugesetzt wird , beträgt 0,01 bis 0,3 Gew.-% bezogen auf die Papiermasse . Setzt man der Papiermasse epoxidiertes höheres Fettsäureamid in Mengen unter 0,01 Gew.-% bezogen auf die Papier­masse zu , so wird das Eindringen der photogra­phischen Bäder in das Papier nicht ausreichend ver­hindert . Erhöht man die Menge an epoxidiertem höheren Fettsäureamid auf über 0,3 Gew.-% bezogen auf die Papiermasse , so verliert das Papier an innerer Festigkeit , was sich negativ auf die Eigen­schaften als Träger für photographische Schichten auswirkt .According to the invention, an epoxidized higher fatty acid amide is further added to the paper pulp. The fatty acid residues of the epoxidized higher fatty acid amide consist of alkyl groups with 14 to 30 carbon atoms.
In an acid-sized paper pulp, the ratio of epoxidized higher fatty acid amide to fatty acid or the fatty acid salt is 0.01: 1 to 0.2: 1.
If alkyl ketene dimer is additionally used, the ratio of epoxidized higher fatty acid amide to alkyl ketene dimer to fatty acid or fatty acid salt is 0.02: 0.2: 1 to 0.15: 0.4: 1. The total amount of epoxidized higher fatty acid amide which is added to the sizing mixture used according to the invention is 0.01 to 0.3% by weight, based on the paper pulp. If epoxidized higher fatty acid amide is added to the paper pulp in amounts below 0.01% by weight, based on the paper pulp, the penetration of the photographic baths into the paper is not sufficiently prevented. If the amount of epoxidized higher fatty acid amide is increased to over 0.3% by weight, based on the pulp, the paper loses its internal strength, which has a negative effect on the properties as a support for photographic layers.

Der Papiermasse wird weiterhin anionisches und kat­ionisches Polyacrylamid zugegeben . Das Verhältnis von anionischem zu kationischem Polyacrylamid be­trägt 40/60 bis 60/40 , bevorzugt genau 50/50 . Die zugesetzte Gesamtmenge beträgt 0,2 bis 2,0 Gew.-%, vorzugsweise 0,4 bis 1,4 Gew.-%, bezogen auf die Papiermasse .Anionic and cationic polyacrylamide are also added to the paper pulp. The ratio of anionic to cationic polyacrylamide is 40/60 to 60/40, preferably exactly 50/50. The total amount added is 0.2 to 2.0% by weight, preferably 0.4 to 1.4 wt .-%, based on the pulp.

Beispiele für kationische Polyacrylamide , die erfindungsgemäß verwendet werden , sind gemäß Mannich modifizierte Produkte von Polyacrylamiden , Hofmann-Abbauprodukte von Polyacrylamiden , Copolymerisationsprodukte zwischen Acrylamiden und Ethylenimin , Copolymerisate aus Acrylamid mit einem kationischen Monomeren , wie Dimethylamino­ethylmethacrylat , in Form der sauren Salze organi­scher oder Mineralsäuren oder in quarternierter Form mit Methylchlorid oder Dimethylsulfat , oder Ester wie z.B. Diethylaminoethylacrylester . Das Molekulargewicht liegt in einem Bereich von 500 000 bis 2.000.000 , bevorzugt von 1.000.000 bis 1.500.000 .Examples of cationic polyacrylamides which are used according to the invention are products of polyacrylamides modified according to Mannich, Hofmann degradation products of polyacrylamides, copolymerization products between acrylamides and ethyleneimine, copolymers of acrylamide with a cationic monomer, such as dimethylaminoethyl methacrylate, in the form of the acidic salts of organic or mineral acids or in quaternized form with methyl chloride or dimethyl sulfate, or esters such as Diethylaminoethyl acrylate. The molecular weight is in a range from 500,000 to 2,000,000, preferably from 1,000,000 to 1,500,000.

Erfindungsgemäß verwendete anionische Polyacrylamide sind z.B. teilweise hydrolysierte Produkte von Poly­acrylamiden, Acrylamid/Acrylsäure-Copolymerisate bzw. deren Salze , (Meth-)Acrylamid/Methacrylsäure-­Copolymerisate bzw. deren Salze , (Meth-)Acrylamid-­(Meth-)Acrylsäure/Acrylnitril-Copolymerisate bzw. deren Salze und (Meth-)Acrylamid/(Meth-)Acrylsäure­ester-Copolymerisate bzw. deren Verseifungsprodukte. Das Molekulargewicht liegt in dem Bereich von 500 000 bis 2.000.000 , bevorzugt von 1.000.000 bis 1.500.000 .Anionic polyacrylamides used according to the invention are e.g. partially hydrolyzed products of polyacrylamides, acrylamide / acrylic acid copolymers or their salts, (meth) acrylamide / methacrylic acid copolymers or their salts, (meth) acrylamide (meth) acrylic acid / acrylonitrile copolymers or their salts and (Meth) acrylamide / (meth) acrylic ester copolymers or their saponification products. The molecular weight is in the range from 500,000 to 2,000,000, preferably from 1,000,000 to 1,500,000.

Es wurde gefunden , daß sich die Verwendung der Kombination von Fettsäure und/oder Fettsäuresalzen , Aluminiumsalzen , eventuell Alkylketendimer , und epoxidiertem höheren Fettsäureamid besonders günstig auf die Verschmutzung der Kanten des Papiers durch die photographischen Bäder auswirkt .It has been found that the use of the combination of fatty acid and / or fatty acid salts, aluminum salts, possibly alkyl ketene dimer, and epoxidized higher fatty acid amide has a particularly favorable effect on the soiling of the edges of the paper by the photographic baths.

Dadurch wird auch die in neuerer Zeit vorherrschende Meinung widerlegt, daß eine gute Innenleimung, die das Papier vor der Permeation der photographischen Bäder schützt, sowie eine hohe innere Festigkeit der Papiere, nur bei neutraler Fahrweise, d. h. mit neutralen Leimungsmitteln im neutralen pH-Bereich, erreicht werden kann.This also refutes the opinion prevailing recently that a good internal sizing, which protects the paper from the permeation of the photographic baths, and a high internal strength of the papers, only with a neutral driving style, i. H. can be achieved with neutral sizing agents in the neutral pH range.

Überraschenderweise bewirkt der weitere Zusatz von anionischem und kationischem Polyacrylamid keine starke Flockung der Fasern, sondern vielmehr eine hochglatte Oberfläche des Papiers bei einem gleichzeitig drastischen Anstieg der inneren Festigkeit. Der Festigkeitsanstieg erwies sich als nicht nur konzentra­tionsabhängig. Zwar konnte generell bei allen eingesetzten Polyacrylamid-Kombinationen ein konzentrationsabhängiger Anstieg der inneren Festigkeit beobachtet werden, jedoch war dieser Festigkeitsgewinn bei gleichen Einsatzmengen, gleichem Mengenverhältnis und gleichen Kettenlängen der Polyacrylamide unterschiedlich.Surprisingly, the further addition of anionic and cationic polyacrylamide does not cause strong flocculation of the fibers, but rather a highly smooth surface of the paper with a simultaneous drastic increase in the internal strength. The increase in strength proved to be not only dependent on the concentration. In general, a concentration-dependent increase in the internal strength could be observed for all polyacrylamide combinations used, but this gain in strength was different with the same amounts used, the same quantity ratio and the same chain lengths of the polyacrylamides.

Es wurde nämlich gefunden, daß die Auswirkungen auf die innere Festigkeit des Papiers darüber hinaus abhängig von dem Acrylat­anteil der verwendeten anionischen Polyacrylamide ist, und zwar handelt es sich nicht um eine lineare Abhängigkeit, d. h. das Maximum der inneren Festigkeit wird nicht bei einem hohen Anteil an anionischen Gruppen erzielt. Es wird vielmehr dann erhalten, wenn der Anteil der anionischen Gruppen im anioni­schen Polyacrylamid 5 bis 20 % beträgt.It has been found that the effects on the internal strength of the paper are also dependent on the acrylate content of the anionic polyacrylamides used, and this is not a linear dependence, i. H. the maximum internal strength is not achieved with a high proportion of anionic groups. Rather, it is obtained when the proportion of anionic groups in the anionic polyacrylamide is 5 to 20%.

Die erfindungsgemäß verwendeten Polyacrylamide können als Mischung oder einzeln der Papiermasse zugegeben werden. Bevorzugt wird die einzelne Zugabe.The polyacrylamides used according to the invention can be added to the paper pulp as a mixture or individually. The individual addition is preferred.

Für die Verwendung als photographischer Träger kann das Papier neben einer Innerleimung in der Papier­masse außerdem noch mit einer Oberflächenleimung versehen sein , die z.B. aus einem Stärke- oder Polyvinylalkoholstrich besteht , der aus wäßriger Lösung mit einem bekannten Auftragsverfahren auf die Papierbahn aufgebracht wird .
Das Papier kann außerdem ein- oder beidseitig mit einer Polyolefinüberzugsschicht versehen werden , die ein lichtreflektierendes Weißpigment (speziell in der Vorderseitenbeschichtung) sowie gegebenen­falls Farbpigmente , optische Aufheller und/oder andere Zusätze wie antistatisch wirkende Verbin­dungen , Dispergierhilfsmittel für das Weißpigment und Antioxidantien enthalten kann . Die Polyolefin­überzugsschicht wird in üblicher Weise durch Extrusionsbeschichtung aufgebracht .For use as a photographic support, in addition to an inner sizing in the paper pulp, the paper can also be provided with a surface sizing consisting, for example, of a starch or polyvinyl alcohol coating which is applied to the paper web from an aqueous solution using a known application method.
The paper can also be provided on one or both sides with a polyolefin coating layer, which can contain a light-reflecting white pigment (especially in the front coating) and, if appropriate, color pigments, optical brighteners and / or other additives such as antistatic compounds, dispersing aids for the white pigment and antioxidants. The polyolefin coating layer is applied in a conventional manner by extrusion coating.

Das Papier selbst kann neben der erfindungsgemäß verwendeten Mischung noch mineralische oder organische Füllstoffe , Weißpigment , Farbstoff oder Farbpigment , optische Aufheller , Antioxidantien und/oder andere bei der Herstellung photographischer Träger übliche Zusatzstoffe enthalten .In addition to the mixture used according to the invention, the paper itself can also contain mineral or organic fillers, white pigment, dye or color pigment, optical brighteners, antioxidants and / or other additives customary in the production of photographic supports.

Der erfinderische Gedanke wird anhand der nach­folgenden Beispiele verdeutlicht .The inventive idea is illustrated by the following examples.

Beispiel 1example 1

Ein ca. 150 g/m² schweres Papier wird aus einer wäßrigen Zellstoffaufschlämmung (LBKP/NBKP = 2/1) hergestellt, der eine Leimungsmischung folgender Zusammensetzung zugesetzt wurde:
Stearinsäure 1 Gew.-%
Aluminiumsulfat 2 Gew.-%
epoxidiertes höheres Fettsäureamid 0,15 Gew.-%
anionisches und kationisches Poly­acrylamid im Verhältnis von 50/50; Gesamtmenge 1,0 Gew.-%An approx. 150 g / m² heavy paper is made from an aqueous pulp slurry (LBKP / NBKP = 2/1) to which a sizing mixture of the following composition has been added:
Stearic acid 1% by weight
Aluminum sulfate 2% by weight
epoxidized higher fatty acid amide 0.15% by weight
anionic and cationic polyacrylamide in the ratio of 50/50; Total amount 1.0% by weight

Es wurden anionische Polyacrylamide mit folgenden Anteilen an anionischen Gruppen verwendet:

  • 1a 5 %
  • 1b 10 %
  • 1c 20 %
  • 1d 40 %
  • 1e 60 %
Anionic polyacrylamides with the following proportions of anionic groups were used:
  • 1a 5%
  • 1b 10%
  • 1c 20%
  • 1d 40%
  • 1e 60%

Das aus dieser Mischung hergestellte Papier wird in üblicher Weise beidseitig mit Polyethylen extrusionsbeschichtet.The paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.

Beispiel 2Example 2

Ein ca. 150 g/m² schweres Papier wird aus einer wäßrigen Zellstoffaufschlämmung (LBKP/NBKP = 2/1) hergestellt, der eine Leimungsmischung folgender Zusammensetzung zugesetzt wurde:
Stearinsäure 3 Gew.-%
Aluminiumsulfat 6 Gew.-%
Alkyletendimer 0,6 Gew.-%
epoxidiertes höheres Fettsäureamid 0,1 Gew.-%
anionisches und kationisches Poly­acrylamid im Verhältnis 50/50; Gesamtmenge 1,0 Gew.-%An approximately 150 g / m² heavy paper is made from an aqueous pulp slurry (LBKP / NBKP = 2/1), to which a sizing mixture of the following composition was added:
Stearic acid 3% by weight
Aluminum sulfate 6% by weight
Alkyletene dimer 0.6% by weight
epoxidized higher fatty acid amide 0.1% by weight
anionic and cationic polyacrylamide in the ratio 50/50; Total amount 1.0% by weight

Es wurden anionische Polyacrylamide mit folgenden Anteilen an anionischen Gruppen verwendet:

  • 2a 5 %
  • 2b 10 %
  • 2c 20 %
  • 2d 40 %
  • 2e 60 %
Anionic polyacrylamides with the following proportions of anionic groups were used:
  • 2a 5%
  • 2b 10%
  • 2c 20%
  • 2d 40%
  • 2e 60%

Das aus dieser Mischung hergestellte Papier wird in üblicher Weise beidseitig mit Polyethylen extrusionsbeschichtet.The paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.

Beispiel 3Example 3

Ein ca. 175 g/m² schweres Papier wird aus einer wäßrigen Zellstoffaufschlämmung (LBKP/NBKP = 1/1) hergestellt, der eine Leimungsmischung folgender Zusammensetzung zugesetzt wurde:
Natriumstearat 2 Gew.-%
Aluminiumtrichlorid 4 Gew.-%
anionisches und kationisches Poly­acrylamid im Verhältnis 40/60; Anteil an anionischen Gruppen im anio­nischen Polyacrylamid: 10 %; Gesamtmenge 0,3 Gew.-%
epoxidiertes höheres Fettsäureamid:

  • 3a 0,005 Gew.-%
  • 3b 0,01 Gew.-%
  • 3c 0,04 Gew.-%
  • 3d 0,1 Gew.-%
  • 3e 0,3 Gew.-%
  • 3f 0,5 Gew.-%
An approximately 175 g / m² heavy paper is made from an aqueous pulp slurry (LBKP / NBKP = 1/1), to which a sizing mixture of the following composition was added:
Sodium stearate 2% by weight
Aluminum trichloride 4% by weight
anionic and cationic polyacrylamide in the ratio 40/60; Proportion of anionic groups in the anionic polyacrylamide: 10%; Total amount 0.3% by weight
epoxidized higher fatty acid amide:
  • 3a 0.005% by weight
  • 3b 0.01% by weight
  • 3c 0.04% by weight
  • 3d 0.1% by weight
  • 3e 0.3% by weight
  • 3f 0.5% by weight

Das aus dieser Mischung hergestellte Papier wird in üblicher Weise beidseitig mit Polyethylen extrusionsbeschichtet.The paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.

Beispiel 4Example 4

Ein ca. 175 g/m² schweres Papier wird aus einer wäßrigen Zellstoffaufschlämmung (LBKP/NBKP = 1/1) hergestellt, der eine Leimungsmischung folgender Zusammensetzung zugesetzt wurde:
Natriumstearat 2 Gew.-%
Aluminiumtrichlorid 4 Gew.-%
epoxidiertes höheres Fettsäureamid 0,1 Gew.-%
anionisches und kationisches Poly­acrylamid im Verhältnis von 60/40; Anteil an anionischen Gruppen im anionischen Polyacrylamid: 10 % in folgenden Gesamtmengen:

  • 4a 0,2 Gew.-%
  • 4b 0,4 Gew.-%
  • 4c 0,8 Gew.-%
  • 4d 1,0 Gew.-%
  • 4e 2,0 Gew.-%
An approximately 175 g / m² heavy paper is produced from an aqueous pulp slurry (LBKP / NBKP = 1/1), to which a sizing mixture of the following composition was added:
Sodium stearate 2% by weight
Aluminum trichloride 4% by weight
epoxidized higher fatty acid amide 0.1% by weight
anionic and cationic polyacrylamide in the ratio of 60/40; Proportion of anionic groups in the anionic polyacrylamide: 10% in the following total amounts:
  • 4a 0.2% by weight
  • 4b 0.4% by weight
  • 4c 0.8% by weight
  • 4d 1.0% by weight
  • 4e 2.0% by weight

Das aus dieser Mischung hergestellte Papier wird mit Poly­ethylen in üblicher Weise extrusionsbeschichtet.The paper made from this mixture is extrusion coated with polyethylene in the usual way.

Beispiel 5Example 5

Ein ca. 175 g/m² schweres Papier wird aus einer wäßrigen Zellstoffaufschlämmung (LBKP/NBKP = 1/1) hergestellt, der eine Leimungsmischung folgender Zusammensetzung zugesetzt wurde:

  • 5a: Natriumstearat 1,5 Gew.-%
    Aluminiumtrichlorid 3 Gew.-%
    Alkylketendimer 0,6 Gew.-%
    epoxidiertes höheres Fettsäureamid 0,22 Gew.-%
    anionisches und kationisches Poly­acrylamid im Verhältnis 40/60; Anteil an anionischen Gruppen im anionischem Polyacrylamid: 10 %; Gesamtmenge: 0,4 Gew.-%
  • 5b: Natriumstearat 2 Gew.-%
    Aluminiumtrichlorid 4 Gew.-%
    Alkylketendimer 0,4 Gew.-%
    epoxidiertes höheres Fettsäureamid 0,04 Gew.-%
    anionisches und kationisches Poly­acrylamid im Verhältnis 60/40; Anteil an anionischen Gruppen im anionischen Polyacrylamid: 10 %; Gesamtmenge: 1,5 Gew.-%
An approximately 175 g / m² heavy paper is produced from an aqueous pulp slurry (LBKP / NBKP = 1/1), to which a sizing mixture of the following composition was added:
  • 5a : sodium stearate 1.5% by weight
    Aluminum trichloride 3% by weight
    Alkyl ketene dimer 0.6% by weight
    epoxidized higher fatty acid amide 0.22% by weight
    anionic and cationic polyacrylamide in the ratio 40/60; Proportion of anionic groups in the anionic polyacrylamide: 10%; Total: 0.4% by weight
  • 5b : sodium stearate 2% by weight
    Aluminum trichloride 4% by weight
    Alkyl ketene dimer 0.4% by weight
    epoxidized higher fatty acid amide 0.04% by weight
    anionic and cationic polyacrylamide in the ratio 60/40; Proportion of anionic groups in the anionic polyacrylamide: 10%; Total: 1.5% by weight

Das aus dieser Mischung hergestellte Papier wird mit einem Oberflächenstrich folgender Zusammensetzung versehen:
Wasser 1000 g
Crotonsäure-modifizierter Polyvinylalkohol Verseifungsgrad: 99 %
Carboxylgruppenanteil 3,1 mol-% 40 g
Zirkoniumammoniumcarbonat 8 g
Natriumchlorid 20 gThe paper made from this mixture is provided with a surface coating of the following composition:
Water 1000 g
Crotonic acid-modified polyvinyl alcohol degree of saponification: 99%
Carboxyl group content 3.1 mol% 40 g
Zirconium ammonium carbonate 8 g
Sodium chloride 20 g

Die Auftragsmenge beträgt 2 g/m². Das behandelte Papier wird getrocknet und mit Polyethylen in üblicher Weise extrusions­beschichtet.The order quantity is 2 g / m². The treated paper is dried and extrusion coated with polyethylene in the usual way.

Vergleichsbeispiel 1Comparative Example 1

Ein ca. 170 g/m² schweres Papier wird nach Beispiel 4 der DOS 32 16 840 aus einer Zellstoffaufschlämmung (LBKP/NBKP = 2/1) hergestellt, der eine Leimungsmischung folgender Zusammensetzung zugesetzt wurde:
Alkylketendimer 0,4 Gew.-%
Polyamid-Polyamin-Epichlorhydrin 0,5 Gew.-%
kationisches Polyacrylamid 0,5 Gew.-%
anionisches Polyacrylamid 0,5 Gew.-%An approximately 170 g / m² heavy paper is produced according to Example 4 of DOS 32 16 840 from a pulp slurry (LBKP / NBKP = 2/1), to which a sizing mixture of the following composition was added:
Alkyl ketene dimer 0.4% by weight
Polyamide-polyamine-epichlorohydrin 0.5% by weight
cationic polyacrylamide 0.5% by weight
anionic polyacrylamide 0.5% by weight

Das aus dieser Mischung hergestellte Papier wird in üblicher Weise beidseitig mit Polyethylen extrusionsbeschichtet.The paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.

Vergleichsbeispiel 2Comparative Example 2

Ein ca. 170 g/m² schweres Papier wird nach Beispiel 2 der DOS 32 16 841 aus einer wäßrigen Zellstoffaufschlämmung (LBKP/NBKP = 1/1) hergestellt, der eine Leimungsmischung folgender Zusammensetzung zugesetzt wurde:
Alkylketendimer 0,7 Gew.-%
Polyamid-Polyamin-Epichlorhydrin 0,5 Gew.-%
kationisches Polyacrylamid 0,7 Gew.-%An approximately 170 g / m² heavy paper is produced according to Example 2 of DOS 32 16 841 from an aqueous cellulose slurry (LBKP / NBKP = 1/1), to which a sizing mixture of the following composition was added:
Alkyl ketene dimer 0.7% by weight
Polyamide-polyamine-epichlorohydrin 0.5% by weight
cationic polyacrylamide 0.7% by weight

Das aus dieser Mischung hergestellte Papier wird in üblicher Weise beidseitig mit Polyethylen extrusionsbeschichtet.The paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.

Vergleichsbeispiel 3Comparative Example 3

Ein ca. 150 g/m² schweres Papier wird nach Beispiel 1 der DOS 32 10 621 aus einer wäßrigen Zellstoffaufschlämmung hergestellt, der eine Leimungsmischung folgender Zusammen­setzung zugesetzt wurde:
Alkylketendimer 0,5 Gew.-%
epoxidiertes höheres Fettsäureamid 0,3 Gew.-%
kationische Stärke 2,5 Gew.-%
anionisches Polyacrylamid 0,3 Gew.-%An approx. 150 g / m² heavy paper is produced according to Example 1 of DOS 32 10 621 from an aqueous cellulose slurry, to which a sizing mixture of the following composition has been added:
Alkyl ketene dimer 0.5% by weight
epoxidized higher fatty acid amide 0.3% by weight
cationic starch 2.5% by weight
anionic polyacrylamide 0.3% by weight

Das aus dieser Mischung hergestellte Papier wird in üblicher Weise beidseitig mit Polyethylen extrusionsbeschichtet.The paper produced from this mixture is extrusion-coated on both sides with polyethylene in the usual way.

Vergleichsbeispiel 4Comparative Example 4

Ein ca. 150 g/m² schweres Papier wird aus einer wäßrigen Zellstoffaufschlämmung (LBKP/NBKP = 2/1) hergestellt, der eine Leimungsmischung folgender Zusammensetzung zugesetzt wurde:

  • 4a: Stearinsäure 1 Gew.-%
    Aluminiumsulfat 2 Gew.-%
    anionisches und kationisches Poly­acrylamid im Verhältnis 50/50;
    Anteil an anionischen Gruppen im anionischen Polyacrylamid: 10 %;
    Gesamtmenge 1,0 Gew.-%
  • 4b: Stearinsäure 1 Gew.-%
    Aluminiumsulfat 2 Gew.-%
    epoxidiertes höheres Fettsäureamid 0,15 Gew.-%
  • 4c: nach Beispiel 5a, jedoch ohne das epoxidierte höhere Fettsäureamid
  • 4d: nach Beispiel 5a, jedoch ohne anionisches und kationisches Polyacrylamid
An approximately 150 g / m² heavy paper is made from an aqueous pulp slurry (LBKP / NBKP = 2/1), to which a sizing mixture of the following composition was added:
  • 4a : stearic acid 1% by weight
    Aluminum sulfate 2% by weight
    anionic and cationic polyacrylamide in the ratio 50/50;
    Proportion of anionic groups in the anionic polyacrylamide: 10%;
    Total amount 1.0% by weight
  • 4b : stearic acid 1% by weight
    Aluminum sulfate 2% by weight
    epoxidized higher fatty acid amide 0.15% by weight
  • 4c : according to Example 5a , but without the epoxidized higher fatty acid amide
  • 4d : according to Example 5a , but without anionic and cationic polyacrylamide

Das aus dieser Mischung hergestellte Papier wird mit Poly­ethylen in üblicher Weise extrusionsbeschichtet.The paper made from this mixture is extrusion coated with polyethylene in the usual way.

Prüfung der TrägermaterialienExamination of the carrier materials

Sowohl das Papier wie auch der durch beidseitige Poly­ethylenextrusion hergestellte Papierträger für photogra­phische Schichten werden Prüfungen unterworfen .Both the paper and the paper support for photographic layers produced by double-sided polyethylene extrusion are subjected to tests.

Prüfung 1. : Messung der Oberflächenglätte (Oberflächenzahl) Test 1 .: Measurement of surface smoothness (number of surfaces)

Die Prüfung erfolgt an dem unbeschichteten Papier nach der in der deutschen Patentanmeldung P 34 26 782.4-52 beschriebenen Prüfmethode .The test is carried out on the uncoated paper using the test method described in German patent application P 34 26 782.4-52.

Prüfung 2. : Bestimmung des Kanteneindringens Exam 2 . : Determination of edge penetration

Das mit Polyethylen beschichtete Papier wird einem simulierten photographischen Entwicklungsprozeß mit einem Benzylakohol enthaltenden handelsüblichen Entwickler bei einer Temperatur von etwa 30°C und über eine Zeitdauer von 25 Minuten unterworfen . An beiden Kanten des Prüfstücks wird das Eindringen der photographischen Bäder mit einer Meßlupe ausgemessen . Die Meßwerte werden als Kanteneindringen (KE) in mm angegeben .The polyethylene coated paper is subjected to a simulated photographic development process with a commercial developer containing benzyl alcohol at a temperature of about 30 ° C and for a period of 25 minutes. The penetration of the photographic baths is measured on both edges of the test piece with a measuring magnifier. The measured values are given as edge penetration (KE) in mm.

Prüfung 3. : Bestimmung der inneren Festigkeit (Spaltfestigkeit) Test 3 .: Determination of the internal strength (gap strength)

Die Prüfung erfolgt an dem mit Polyethylen beschichteten Papier nach der in TAPPI RC 308 angegebenen Methode mit dem Internal Bond Impact Tester Model B .
Die Meßwerte werden in 1/1000 Fuß x Pfund angegeben .

Figure imgb0001
Figure imgb0002
 The test is carried out on the paper coated with polyethylene according to the method specified in TAPPI RC 308 with the Internal Bond Impact Tester Model B.
The measurements are reported in 1/1000 feet x pounds.
Figure imgb0001
Figure imgb0002

Bewertung der ErgebnisseEvaluation of the results

Die Beispiele 1 bis 5 verdeutlichen den erfindungsgemäßen Effekt. Die Prüfwerte in Spalte 3 (Prüfung 3) zeigen, daß das Optimum in bezug auf die innere Festigkeit des Papiers bei einem Anteil an anionischen Gruppen im anionischen Poly­acrylamid von 10 % liegt.Examples 1 to 5 illustrate the effect according to the invention. The test values in column 3 (test 3) show that the optimum in terms of the internal strength of the paper is 10% with an anionic group in the anionic polyacrylamide.

Die Gegenüberstellung zu den im Stand der Technik beschrie­benen Leimungsmischungen (Vergleichsbeispiele 1 bis 4) ver­deutlicht die Verbesserung der Oberflächenglätte, die bei der Verwendung der erfindungsgemäßen Leimungsmischung erhal­ten wird (Spalte 1 der Prüfergebnisse, Prüfung 1).The comparison with the sizing mixtures described in the prior art (comparative examples 1 to 4) illustrates the improvement in the surface smoothness which is obtained when using the sizing mixture according to the invention (column 1 of the test results, test 1).

Die Spalte 2 der Prüfergebnisse macht deutlich, daß in bezug auf die Leimung bei der Verwendung der erfindungsgemäßen Leimungsmischung keine Verschlechterung gegenüber denen im Stand der Technik beschriebenen Leimungsmischungen auftreten. Das herrschende Vorurteil, daß nämlich eine gute Leimung nur unter Verwendung neutraler Leimungsmittel erreicht werden kann, wird hiermit widerlegt.Column 2 of the test results makes it clear that, with regard to the sizing, no deterioration occurs compared to the sizing mixtures described in the prior art when using the sizing mixture according to the invention. The prevailing prejudice that a good sizing can only be achieved using neutral sizing agents is hereby refuted.

Claims (7)

1. Polyolefinharz-beschichteter wasserfester fotografischer Papierträger, dessen Papier aus einer Papiermasse gebildet ist, die Fettsäure und/oder Fettsäuresalz und Aluminiumsalz sowie gegebenenfalls ein Alkylketendimer enthält, dadurch gekennzeichnet, daß die Papiermasse außerdem anionisches und kationisches Polyacrylamid im Verhältnis 40 : 60 bis 60 : 40 sowie ein epoxidiertes höheres Fettsäureamid enthält, und daß der Anteil der anionischen Gruppen im anionischen Polyacrylamid 5 bis 20 % beträgt.1. Polyolefin resin-coated, waterproof photographic paper support, the paper of which is formed from a paper pulp which contains fatty acid and / or fatty acid salt and aluminum salt and optionally an alkyl ketene dimer, characterized in that the paper pulp also contains anionic and cationic polyacrylamide in a ratio of 40:60 to 60: 40 and an epoxidized higher fatty acid amide, and that the proportion of anionic groups in the anionic polyacrylamide is 5 to 20%. 2. Fotografischer Papierträger gemäß Anspruch 1, dadurch gekennzeichnet, daß der Anteil der anionischen Gruppen im anionischen Polyacrylamid etwa 10 % beträgt.2. Photographic paper support according to claim 1, characterized in that the proportion of anionic groups in the anionic polyacrylamide is about 10%. 3. Fotografischer Papierträger gemäß Anspruch 1, dadurch gekennzeichnet, daß die Polyacrylamide in einer Gesamtmenge von 0,2 bis 2,0 Gew.-%, bezogen auf den Faserstoff, enthalten sind.3. Photographic paper support according to claim 1, characterized in that the polyacrylamides are contained in a total amount of 0.2 to 2.0 wt .-%, based on the fiber. 4. Fotografischer Papierträger nach Anspruch 3, dadurch gekennzeichnet, daß die Polyacrylamide in einer Gesamtmenge von 0,4 bis 1,4 Gew.-%, bezogen auf den Faserstoff, enthalten sind.4. Photographic paper support according to claim 3, characterized in that the polyacrylamides are contained in a total amount of 0.4 to 1.4 wt .-%, based on the fiber. 5. Fotografischer Papierträger gemäß Anspruch 1, dadurch gekennzeichnet, daß das Verhältnis von epoxidiertem höherem Fettsäureamid zu Fettsäure bzw. Fettsäuresalz 0,01 : 1 bis 0,2 : 1 beträgt und der Gehalt an epoxidiertem höherem Fett­säureamid 0,01 bis 0,3 Gew.-% bezogen auf Faserstoff ist.5. Photographic paper support according to claim 1, characterized in that the ratio of epoxidized higher fatty acid amide to fatty acid or fatty acid salt is 0.01: 1 to 0.2: 1 and the content of epoxidized higher fatty acid amide is 0.01 to 0.3 wt .-% is based on fiber. 6. Fotografischer Papierträger gemäß Anspruch 1, dadurch gekennzeichnet, daß das epoxidierte höhere Fettsäureamid Alkylketten mit der Kettenlänge von C₁₄ bis C₃₀ enthält.6. Photographic paper support according to claim 1, characterized in that the epoxidized higher fatty acid amide contains alkyl chains with the chain length of C₁₄ to C₃₀. 7. Fotografischer Papiertärger gemäß Anspruch 1, dadurch gekennzeichnet, daß das Verhältnis von epoxidiertem Fett­säureamid zu Alkylketendimer zu Fettsäure bzw. Fettsäure­salz 0,02 : 0,2 : 1 bis 0,15 : 0,5 : 1 beträgt.7. Photographic paper tester according to claim 1, characterized in that the ratio of epoxidized fatty acid amide to alkyl ketene dimer to fatty acid or fatty acid salt is 0.02: 0.2: 1 to 0.15: 0.5: 1.
EP87101089A 1986-03-03 1987-01-27 Water-resistant photographic paper support Expired - Lifetime EP0235564B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3606806 1986-03-03
DE3606806A DE3606806C1 (en) 1986-03-03 1986-03-03 Waterproof photographic paper carrier

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EP0235564A1 true EP0235564A1 (en) 1987-09-09
EP0235564B1 EP0235564B1 (en) 1990-09-12

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EP87101089A Expired - Lifetime EP0235564B1 (en) 1986-03-03 1987-01-27 Water-resistant photographic paper support

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US (1) US4808267A (en)
EP (1) EP0235564B1 (en)
JP (1) JPH0687130B2 (en)
DE (2) DE3606806C1 (en)
ES (1) ES2000047B3 (en)
GR (1) GR900300061T1 (en)

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EP0356531A1 (en) * 1988-07-28 1990-03-07 FELIX SCHOELLER JR. GMBH & CO. KG Water-resistant photographic-paper support

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JP2711483B2 (en) * 1991-03-20 1998-02-10 富士写真フイルム株式会社 Photographic paper support
AU1917492A (en) * 1991-05-03 1992-12-21 Henkel Corporation Wet strength resin composition
DE4428940C2 (en) 1994-08-16 1998-04-16 Schoeller Felix Jun Foto Base paper of a support for photographic recording materials
FI20000957A (en) * 2000-04-20 2001-10-21 Raisio Chem Oy Additive for paper manufacture, its manufacture and use
WO2005118953A1 (en) * 2004-06-03 2005-12-15 Fuji Photo Film B.V. Pigment coated paper base
EP2999818A4 (en) * 2013-05-22 2017-01-11 Dow Global Technologies LLC Paper composition and process for making the same

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GB2107610A (en) * 1981-10-21 1983-05-05 Fuji Photo Film Co Ltd Photographic support
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EP0356531A1 (en) * 1988-07-28 1990-03-07 FELIX SCHOELLER JR. GMBH & CO. KG Water-resistant photographic-paper support

Also Published As

Publication number Publication date
JPH0687130B2 (en) 1994-11-02
DE3764826D1 (en) 1990-10-18
US4808267A (en) 1989-02-28
GR900300061T1 (en) 1991-07-31
ES2000047A4 (en) 1987-11-01
JPS62211644A (en) 1987-09-17
DE3606806C1 (en) 1987-06-25
ES2000047B3 (en) 1991-02-16
EP0235564B1 (en) 1990-09-12

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